Treatment of protein-containing textile materials and products thereof



Patented Mar. 7, 1950 TREATMENT OF PROTEIN- CONTAINING TEXTILE MATERIALSAND PRODUCTS THEREOF Edward L. Kropa, Old Greenwich, and Arthur S.Nyqnist, Cos Cob, Com, minors to American Cyanamid Company, New York, N.1., a corporation of Maine No Drawing. Application October 17, 1940Serial No. 703,708

13 Claims.

This invention relates to the treatment of protein-containing textilematerials and to the products thereof. More particularly, the inventionis concerned with a process of treating protein-containing textilematerials, for example wool and wool-containing fabric and other textilematerials, to impart improved properties thereto by treating, moreparticularly impregnating or coating and impregnating, the textilematerial with a composition comprising a reactive product ofpolymerization of a polymerizable mixture including, by weight, fromabout 2 to 20% of maleic anhydride and from about 98 to 80% of a loweralkyl ester of acrylic acid that contains from one to four carbon atoms,inclusive, in the alkyl grouping thereof, e. g., ethyl acrylate. Theresulting textile material is heated at a temperature (e. g., at about200 to 300 F. or slightly above) and for a period of time sufilcient tocure the said polymerization product substantially completely. The curedpolymerization product is substantially water-insoluble.

Protein-containing textile materials, for instance wool-containingtextile materials such as loose wool itself and yarns, threads andwoven, felted and knitted cloth composed of or containing wool have avery undesirable tendency to felt and shrink when subjected to ordinarywashing operations. The tendency of these protein-containing textilematerials to felt and shrink is generally due to curling andintertwining of the protein fibers as the fabrics are wetted andsubjected to the mechanical movements of the washing process. As aresult, the textile material becomes more closely compacted, thicker andhas a considerably reduced area.

A number of different methods have been proposed for the treatment oftextile materials formed of or containing wool or other protein fibersin order to prevent or decrease felting and shrinking. In many casessuch reduction in felting and shrinking tendencies has been obtained atthe sacrifice of some other desirable property of the material. Sometreatments damage the fiber and reduce the wearing qualities whileothers impart an undesirable harshness to the fabric. Other treatmentsare not permanently efiective and may even cause an ultimate increase inshrinkage. Still other shrink-proofing methods are diflicult to applywith uniformity and create hazards to the workers involved in theirapplications.

The present invention is based on our discovery that protein-containingtextile materials, e. g., wool and wool-containing textile materials,when treated with a composition comprising a reactive product ofpolymerization (or copolymer) of a polymerizable mixture includingmaleic anhydride and a lower alkyl ester of acrylic acid, e. g., ethylacrylate, in the proportions by weight set forth in the first paragraphof this specification. yield a treated material which has excellentshrinkage resistance, increased tensile strength, a soft feeling to thetouch, and a permanent finish which remains after laundering. Forexample, when a toluene solution of a soluble copolymer of maleicanhydrlde and ethyl acrylate (10 parts by weight maleic anhydride andparts by weight ethyl acrylate) was applied to a piece of woolen goodsand the treated goods was heated to evaporate the solvent and to curethe copolymer substantially completely, the treated cloth had a softhand, a substantially permanent finish, and even after five launderings(10 minutes each in a soap solution followed by drying) and a finalwashing of 1 hour in a soap solution showed a shrinkage of only 8.3%. Inmarked contrast, untreated woolen cloth when similarly laundered for thesame number of times showed a shrinkage of 39.4%. Furthermore, thetensile strength of the treated cloth was considerably enhanced, beingat least about 35% stronger than the untreated fabric. It was quiteunexpected and unpredictable that such copolymer compositions wouldimpart such improved shrinkage resistance and tensile strength to aprotein-containing textile material, specifically a woolen fabric. Evenmore surprising was the fact that this shrinkage resistance was impartedto the woolen goods without materially lessening its softness to thetouch.

By employing the maleic anhydride-acrylate copolymer compositions of thekind with which this invention is concerned, it is possible to obtainequally as good or better control of the shrinkage oi, for example, woolthan is possible by the use of conventional treating materials and at alower cost since the copolymer used is relatively inexpensive. Ourcopolymer compositions have the further advantage thatprotein-containing textile materials, more particularly wool-containingtextile materials, which have been treated therewith quickly reach apoint of maximum shrinkage upon repeated launderings, whereas the sametextiles when untreated or when treated with some of the prior treatingmaterials show increasingly higher percentage increases in shrinkageupon further laundering. This also was quite surprising and unexpectedand in no way could have been predicted.

spaces Another advantage from the use of our copolymer compositions inpracticing the present invention is that, if desired, a somewhat lesseramount of treating material may be employed than is cutomarily requiredin the treatment of wool-containing textiles with most conventionaltreating materials. For instance, in the case of wool as much as about16% of conventional treating material may be required in order to obtainsatisfactory shrinkage and crease control of the woolen fabric, whereaswith our copolymer compositions satisfactory results usually areobtained with about 8 or 10% or less of the copolymer. The use of higheramounts, however, for example as much as or by weight of the untreatedmaterial, or even higher (e. g., or of the copolymer is not precluded,and in some cases even may be desirable, for instance when it is desiredto provide a weighted proteincontaining fabric.

The reactive copolymers used in practicing this invention are preparedby mixing maleic anhydride with a lower alkyl ester of acrylic acid thatcontains from one to four carbon atoms, inclusive, in the alkyl groupingthereof, e. g., methyl acrylate, ethyl acrylate, propyl acrylate,isopropyi acrylate, butyl acrylate, isobutyl acrylate, etc., in thepercentage proportions hereinbefore given. The mixed ingredients arecopolymerized under anhydrous conditions. Copolymerization may beeilected under, for example, the influence of ultra-violet light, withor without heat and with or without a polymerization catalyst such, forinstance, as benzoyl peroxide or other organic peroxide. If desired, themixed ingredients may be copolymerized in solution state, for example,in solution in an inert organic solvent, e. g., toluene, benzene,xylene, dioxane, ethers (e. g., dibutyl ether), esters (e. g., butylacetate), chlorobenzene, ethylene dichloride, ketones (e. g., methylethyl ketone), etc. The temperature of copolymerization may be varied asdesired or as conditions may require, but ordinarily will be within therange of from about 20 to about 150 0. when copolymerization is effectedin the absence of a solvent. When the mixed ingredients arecopolymerized in solution state, then copolymerization generally iseffected at the boiling temperature of the solution. In all cases, thetemperature of copolymerization is below the decomposition temperatureof the monomeric materials.

In copolymerizing the maleic anhydride with the lower alkyl ester ofacrylic acid, we prefer to use heat and a catalyst for accelerating thepolymerization. Illustrative examples of catalysts that may be employed,in addition to benzoyl peroxide, are inorganic peroxides such, forexample, as barium peroxide, etc.; dialkyl peroxides, e. g., laurylperoxide, stearyl peroxide, di-(tertiary butyl) peroxide, etc.;symmetrical diacyi peroxides, e. g., acetyl peroxide, lauroyl peroxide,stearoyl peroxide, etc.; unsymmetrical or mixed diacyl peroxides, e. g.,acetyl benzoyl peroxide, etc. We prefer to use benzoyl peroxide as thepolymerization catalyst. Any suitable amount of catalyst may be used butin general the catalyst concentration will be within the range of about0.05 to 2 or 3% by weight 01' the mixed copolymerizable materials. Theamount of maleic anhydride in the polymerizable mixture should notexceed about 20% by weight of the mixed ingredients since with higherproportions greater difiiculty is encountered in producing the copolymerand the resulting copolymer when applied to the protein-containingtextile material yields a finished material which is more watersensitive than when the amount of maleic anhydride is 20% or less.Although satisfactory results are obtained when the polymerizablemixture contains as little as about 2 or 3% by weight thereof of maleicanhydride better results are obtained when the maleic anhydride ispresent in larger amount, for example, about 5 to 15% by weight of thepolymerizable mixture. Particularly good results have been obtained withcopolymers produced from a polymerizable mixture of, by weight, about10% of maleic anhydride and about of a lower alkyl ester of acrylicacid, specifically ethyl acrylate.

In eifecting copolymerization of the mixed ingredients it is desirableto avoid the use of any compounds, for example, water, which arereactive with the maleic anhydride. In the case 0! the higher molecularweight, soluble copolymers they may be dissolved in an organic liquidwhich is insoluble in water and an emulsion then formed of the organicsolution of the copolymer. The presence of the organic liquid appears toact as a barrier to prevent water from coming into contact with thecopolymer. In order further to impede the transfer of liquid water andwater vapor one can introduce into the initial solution or dispersion, asmall amount (e. g., from about 0.01 to 10% by weight of the copolymer)of a material which is known to impede the transfer of water vapor, e.g., polyethylene, crystalline products, e. g., paraflln,microcrystalline waxes, etc.

The reactive copolymer composition may be applied to theprotein-containing textile material in any suitable manner. The textllematerial may be contacted with the copolymer in undiluted state or thecopolymer may be applied in the form oi. a solution or dispersionthereof. In all cases the amount of copolymer which is deposited orincorporated in the protein-containing textile material, e. g., wool 01'a wool-containing textile material, is at least about 2% by weight,based on the dry weight of the textile material. The amount will varydepending, for instance, upon the particular protein-containing textilematerial that is undergoing treatment, the particular copolymeremployed, the mode of applieation, the kind of emulsifying agent used ifapplied from a dispersion, whether or not a weighted textile is desired,etc. Ordinarily, however, the amount of copolymer that is incorporatedin the textile material is from about 3 to 15% by weight of the dry,untreated material, but if a weighted textile is wanted it may be muchmore, for example as much as 30% or more by weight of the dry, untreatedtextile.

If the textile material to be treated contains fats, oils or othercontaminants, it is first thoroughly cleaned in any suitable mannerprior to treatment with the copolymer. Various methods may be used inapplying the copolymer. For example, the dry textile material may beimmersed and passed through suitable rolls, as in a padder or mangle, toinsure uniform impregnation and to remove exces copolymer. However, thetextile material may be impregnated or coated and impregnated by othermethods, for example, by spraying or by brushing a solution ordispersion of the copolymer upon the material or by applying thereto aliquid copolymer in undiluated state. Or, the solid copolymer itself maybe combined with the textile material as by passing a sheet or cloth ofthe same, having thereon or therein the copolymer in finely dividedsolid state, between hot rolls. The impregnating operation and theconcentration of the copolymer (in solution, dispersion or other state)are ad- Justed so that the amount of copolymer which is taken up by thetextile material will be most eii'ective and economical in producing thedesired results.

If the reactive polymerization product or copolymer has been applied indissolved or dispersed state to the textile material, the treatedtextile is heated to volatilize the inert, volatile organic liquid (11'the copolymer was applied as a solution thereof) or to volatilize thewater and the inert organic liquid (if the copolymer was applied in theform of an inert organic liquid-water dispersion) and, also, topolymerize the reactive polymerization product or copolymer to asubstantially completely cured condition or state, in which form it iswater-insoluble. During this heat treatment the copolymer may reactchemically with the textile material, more particularly with the proteinmolecules thereof or with free or combined water on or in the textile.The protein may react with the maleic portion of the copolymer to forman amide thereof.

Any suitable elevated temperature may be employed, but in no case shouldthe temperature be so high as to char or otherwise detrimentally affectthe textile material. For instance, with most protein-containingtextiles temperatures within the range of about 200 to 300 F. may beused satisfactorily. Ordinarily, temperatures at or slightly above theboiling point of water or of the particular inert organic liquidemployed are sufficient to effect the desired result. Of course, it willbe understood by those skilled in the art that there is atime-temperature relationship involved: the lower the temperature thelonger the time of heating, and the higher the temperature the shorterthe heating period. The temperature also will vary somewhat with, forinstance, the particular protein-containing textile which has beentreated and the particular copolymer employed.

After the textile material, e. g., wool fabric, has been treated asabove described, it may be given, if desired or necessary, a mildsoaping for a short period before finishing. The textile material thenmay be given the usual finishing treatments required in a particularcase, e. g., decatizr ing, brushing, shearing, pressing, etc.

In order that those skilled in the art better may understand how thepresent invention may be carried into eifeet, the following examples aregiven by way of illustration and not by way of limitation. All parts areby weight.

Example 1 Parts Maleic anhydride 10.0 Ethyl acrylate 90.0 Benzoylperoxide 0.2 Toluene 33.0

The maleic anhydride and benzoyl peroxide were dissolved in the ethylacrylate. Thirty-three parts dry toluene was added. This solution wastransferred to a dropping funnel attached to a three-necked flask whichwas also fitted with a condenser and a thermometer. About parts ofsolution was run into the flask and heating on the steam bath was begun.After 1 minutes of heating, exothermic polymerization commeneed in theflask and after heating for an additional 15 seconds dropwise additionof the solution from the dropping funnel was started.

The addition of the solution was complete after 30 minutes had elapsed.Polymerization proceeded vigorously during most of this time, reaching amaximum temperature of 135 C. during this period. However, continuedexternal heating after the addition resulted in further exothermicpolymerization. Heating was discontinued after 52 minutes elapsed timeand the reaction mass was allowed to cool. One hundred and fifty partstoluene was added after which parts of the solvent was distilled off atreduced pressure in order to remove any unreacted ethyl acrylate. Aportion of the resulting solution of maleie anhydride-ethyl acrylatecopolymer was diluted with additional dry toluene to obtain acomposition containing about 10% of solids.

Part or the maleic anhydride-ethyl acrylate copolymer solution obtainedprior to dilution with toluene to 10% solids content was coagulated byadding an excess of petroleum ether thereto. The coagulated coplyomerwas separated, redissolved in toluene, and coagulated again by adding anexcess of petroleum ether to the toluene solution. The coagulatedcopolymer was separated and washed with petroleum ether. By thistreatment any unreacted maleic anhydride was removed from the reactionproduct. The acid number of the purified copolymer was found to be 108.0The theoretical acid number of a copolymer of ethyl acrylate and maleicanhydride having a 9 to 1 weight ratio of the two components in thecopolymer is 114.5. Since the acid number of the purified copolymer ofthis example was 108, this shows that the ethyl acrylate and maleic anhydride copolymerized in nearly the same ratio in which the monomerswere present in the polymerizable mixture.

A piece of woolen goods was treated with the toluene solution (10%solids content) prepared as above described. The wool sample (9 inchesby 23 inches in size) was immersed in the solution and passed throughrolls to give about 8 or 9% wet pick-up. The sample was framed, airdried for a short period and then heated for 9 minutes at 290 F. Aftercooling to room temperature the sample was removed from the frame,allowed to remain undisturbed for about 16 hours and was then measuredprior to laundering. The method or laundering was a modification of thestandard method of the A. A. T. C. C. and involved heating for 20 to 30minutes at 240 F, while drying after each washing. After a cycle of fiveWashing (10 minutes in soap solution) and drying operations and a finalwashing of 1 hour in a soap solution, the dried, treated cloth showed ashrinkage of only 8.3%. In marked contrast, untreated woolen cloth whensimilarly laundered for the same number of times showed a shrinkage of39.4%. The laundered cloth was pliable and soft. The shrinksee data onthe treated and untreated woolen sample are shown below:

When tested for tensile strength, the treated woolen cloth had a valueof pounds as against '73 pounds for the untreated cloth (A. S. T. M.D-39-39 standard method of test, grab method).

aceacaa Brample 2 Cycle.... 1 2 3 4 5 6 Washing Time in Minutes 10 l i010 l0 10 Percent Shrinkage 0.1 4.4 6.4 6.7 7.2 7.2

Example 3 A maleic anhydride-butyi acrylate reactive copolymer wasprepared in essentially the same manner as described under Example 1,using 10 parts maleic anhydride and 90 parts butyl acrylate, and dioxaneas a solvent instead of toluene. A sample of wool was treated with a 10%dioxane solution of this copolymer as set forth under Example 1. Thefollowing shrinkage data were obtained upon laundering the treatedsample:

Per cent shrinkage After five washing cycles of 10 minutes A maleicanhydride-ethyl acrylate reactive copolymer was prepared in essentiallythe same manner as described under Example 1, using parts maleicanhydride and 95 parts ethyl acrylate. and dioxane as a solvent insteadof toluene. A sample of woolen cloth was treated with a dioxane solutionof this copolymer as set forth under Example 1. After five washingcycles of 10 minutes each as described under Example 1, followed byheating. the dried, treated cloth showed a shrinkage of only 9.2%.

Example 5 Same as Example 4 with the exception that 95 parts butylacrylate instead of ethyl arcylate was used in preparing the reactivecopolymer. After five washing cycles of 10 minutes each as describedunder Example 1, followed by heating, the dried, woolen cloth containingthe water-insoluble maleic anhydride-butyl acrylate copolymer showed ashrinkage of only 8.3%.

Example 6 Same as Example 3 with the exception that 10% tricresylphosphate. based on the solids content of the soluton, was added to the10% di: xane solution of the maleic anhydride-butyl acrylate reactivecopolymer. The following shrinkage data were obtained upon launderingthe treated sample:

Percent shrinkage After five washing cycles of 10 minutes each 8.0 Afterminutes washing 9.7

Example 7 Same as Example 6 with the exception that triphenyl phosphatewas substituted for tricresyl phosphate. The following shrinkage datawere obtained upon laundering the treated sample;

Percent shrinkage After five washin cycles of 10 minutes each 8.0

After 60 minutes washing 9.4

Example 8 In this example a treating solution was used containingapproximately equal parts by volume of a 10% aqueous solution ofmethylated methylol melamine (prepared as described, for example, inPatent No. 2,329,622-Johnstone. Jr., et al.) and a 10% dioxane solutionof a reactive copolymer of 10 parts maleic anhydride and 90 parts ethylacrylate. The following shrinkage data were obtained upon laundering apiece of woolen goods which had been treated with this solution, andthereafter heated to volatilize the solvent and to cure the mixture ofmethylated methylol melamine and reactive maleic anhydride-ethylacrylate copolymer to a substantially water-insoluble condition:

Percent shrinkage After five washing cycles of 10 minutes each 6.4 After60 minutes washing 9.2

Example 9 In this example a treating solution was used containingapproximately equal parts by volume of (1) a 10% solution of a butylatedmethylol melamine dissolved in a 50-50 mixture of butanol and xylene and(2) a 10% dioxane solution of a. reactive copolymer of 10 parts maleicanhydride and parts ethyl acrylate. (The butylated methylol melamine isprepared as described, for example, in the aforementioned patent ofJohnstone, Jr., et al.) The following shrinkage data were obtained uponlaundering a piece of woolen goods which had been treated with thissolution, and thereafter heated to volatilize the solvent and to curethe mixture of butylated methylol melamine and reactive maleicanhydride-ethyl acrylate copolymer to a substantially water-insolublecondition:

Percent shrinkage After five washin cycles of 10 minutes each 4.7 After60 minutes washing 6.9 After five washing cycles of 10 minutes each 9.4

The shrinkage resistance of the treated protrain-containing textilematerial is substantially less when hexyl and higher alkyl esters ofacrylic acid are employed in making the copolymer. This is shown by thefollowing example:

Example 10 A copolymer of 10 parts maleic anhydride and 90 parts hexylacrylate was prepared in essentially the same manner as described underExample 1. After treating a. piece of woolen goods with a dioxanesolution of this copolymer, followed by heating to evaporate the solventand to cure the copolymer substantially completely, the followingshrinkage data were obtained upon laundering the impregnated goods:

Percent shrinkage After five washing cycles of 10 minutes each- 15.0After 60 minutes washing 31.4

The shrinkage resistance of the treated proteincontaining textilematerial also is substantially less when the amount of maleic anhydrideused in making the copolymer is much above about by weight of thepolymerizable mixture. This is shown by the following examples:

Example 11 A copolymer of 30 parts maleic anhydride and 70 parts ethylacrylate was prepared in essentially the same manner as described underExample 1. After treating a piece of woolen goods with a toluenesolution of this copolymer, followed by heating to evaporate the solventand to cure the copolymer, the following shrinkage data were obtainedupon laundering the treated goods:

Percent shrinkage After five washing cycles of 10 minutes each- 22.8After 60 minutes washing 31.9

Example 12 Same as Example 11 with the exception that 40. parts insteadof 30 parts maleic anhydride was used. The following shrinkage data wereobtained upon laundering the treated woolen goods:

Percent shrinkage After five washing cycles of 10 minutes each- 24.4After 60 minutes washing 32.8

It will be understood, of course, by those skilled in the art that ourinvention is not limited to the specific treating compositions describedin Examples 1 to 9, inclusive. Thus, instead of using ethyl acrylate orbutyl acrylate in preparing the reactive copolymer, we may employ anyother lower alkyl ester of acrylic acid, e. g., methyl acrylate, propylacrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate,sec.-butyl acrylate, tert.-butyl acrylate, etc. The acrylic ester andmaleic anhydride should be present in the polymerizabie mixture in aratio by weight corresponding to from about 80 to 98% of the former tofrom about 20 to 2% of the latter. Instead of benzoyl peroxide any otherpolymerization catalyst may be employed, numerous examples of whichhereinbefore have been given.

Illustrative examples of inert, volatile, organic liquids (that is,volatile, organic liquids which are non-reactive with the copolymercomposition) which may be used, if the copolymer is to be applied insolution state or in the form of an inert organic liquid-waterdispersion to the textile material, are benzene, toluene, xylene,dioxane, ethers (e. g., di-isopropyl ether, dibutyl ether, etc), esters(e. g., butyl acetate, etc.), chlorinated hydrocarbons, for instancecarbon tetrachloride, trichloroethylene, ethylene dichloride,chlorobenzenes (e. g., 1,3-dichlorobenzene. etc). ketones (e. g., methylethyl ketone, etc.) petroleum naphtha, etc. If applied in an inertorganic liquid-water dispersion, the inert organic liquid is one whichis immiscible with the water.

It the copolymer is to be applied to the textile material in the form ofa dispersion, specifically an inert organic liquid-water dispersion, anysuitable emulsifying agent may be employed, e. g., the sodium salts ofthe sulfates of a mixture of lauryl and myristyl alcohols, dioctylsodium suifcsuccinate, sodium salts of aliiylaromatic sulfonic acids (e.g., the sodium salt of isopropylnaphthalene sulfonle acid), quaternaryammonium salts (e. g., cetyl dimethyl ammonium chloride), etc. However,the emulsion or dispersion should be such that the copolymer isadequately protected in the dispersion from the action of the water. Insuch an emulsion or dispersion the proportions of water and inertorganic liquid may be varied as desired or as conditions may require,for example from, by volume, about 25 to parts water to about '75 to 25parts inert, volatile organic liquid. The amount of copolymer based onthe total amount of water and inert organic liquid may varyconsiderably, e. g., from about 5 to 20% or more by weight of the totalweight of the water and inert organic liquid. Good results are obtainedusing a solution containing about 10 to 2 by weight thereof of thecopolymer (e. g., a maleic anhydride-ethyl acrylate copolymer) dissolvedin an inert, volatile organic liquid, speciflcally toluene, whichsolution is then emulsifled with about an equal weight of water usingabout 0.5%, by weight of the total water and toluene, of the sodiumsalts of the sulfates of a mixture of lauryl and myristyl alcohols as anemulsifying agent. The amount of emulsifying agent may be variedconsiderably, but ordinarily will be within the range of from about 0.5to 10% by weight of the copolymer in the dispersion.

Our process may be applied in the treatment of various types ofprotein-containing textiles, for instance, those formed of or containingwool, silk, mohair, fur, leather, regenerated fibers or fabrice, e. g.,those produced from casein, soya. bean, collagen, eta; mixtures of suchprotein-containing textiles, and mixtures of such protein-containingtextiles with other types of textiles, for instance, those formed ofcellulose or regenerated cellulose, e. g., cotton, linen, hemp, jute,ramie, sisal, cellulose acetate rayons, viscose rayons, cuprammoniumrayons, etc. In the case of textiles containing mixtures ofprotein-containing and cellulose-containing fibers, the efiect of thetreatment is mostly on the former but the latter also may bebeneficially affected and the copolymer may combine therewith. Ourprocess also may be applied in the treatment of colored textilematerials as well as whites.

The maieic anhydride-acrylate copolymer may be applied alone to thetextile material or it may be applied in combination with othermodifying agents, numerous examples of which are given in our copendingapplication Serial No. 694,156, filed August 30, 1946. The copolymeralso may be used in combination with isocyanate copolymers of the kind.disclosed in our aforementioned copending application and also in ourcopending application Serial No. 694,157, filed August 30, 1946. Ifdesired, the copolymer may be used to supplement or in combination withconventional treating agents in the treatment of textiles to impartimproved properties thereto.

The terms textile and textile material as used generally herein and inthe appended claims include within their meanings filaments, fibers,threads, yarns, etc., as such or in woven, felted or otherwise formedfabrics, sheets, cloths and the like.

What we claim as new and desire to secure by Letters Patent of theUnited States is:

l. A process of treating protein-containing textile material to reducethe felting and shrinking tendencies thereof which comprises (1)treating said textile material solely with a composition comprising areactive product of polymeri- 75 cation of a polymerizable mixtureincluding, by

access:

11 weight, from about 2 to 20% of maleic enhydridc and from about 98 to80% of a lower alkyl ester of acrylic acid that contains from one tofour carbon atoms, inclusive, in the alkyl grouping thereof, and (2)heating the resulting treated material to cure the said polymerizationproduct.

2. A process as in Claim 1 wherein the lower alkyl ester of acrylic acidis ethyl acrylate.

3. A process of reducing the felting and shrinking tendencies ofwool-containing textile material which consists in (1) impregnating sucha material with an inert, volatile organic liquid-water dispersion of areactive product of polymerization of a mixture containing, by weight,from about 2 to 20% of maleic anhydride and from about 98 to 80% of alower alkyl ester of acrylic acid that contains from one to four carbonatoms, inclusive, in the alkyl grouping thereof, the takeup of the saiddispersion being such as to deposit in the said textile material atleast about 2%. based on the dry weight of the textile material, of thesaid polymerization product and (2) heating the resulting treatedmaterial to volatilize the water and the organic liquid from the saiddispersion and to cure the said polymerization product, said curedproduct being substantially water-insoluble.

4. A process of reducing the felting and shrinking tendencies ofwool-containing textile material which consists in 1) impregnating sucha material with a solution of a soluble copolymer dissolved in an inert,volatile organic liquid, said polymer being the product ofpolymerization of a mixture containing, by weight from about 2 to 20% ofmaleic anhydride and from about 98% to 80% of a lower alkyl ester ofacrylic acid that contains from one to four carbon atoms, inclusive, inthe alkyl grouping thereof, the take-up of the said solution being suchas to deposit in the said textile material at least about 2% by weight,based on the dry weight of the textile material, of the said solublecopolymer and (2) heating the resulting treated material to volatilizethe organic liquid from the said solution and to cure the saidpolymerization product, said cured prodnot being substantiallywater-insoluble.

5. A process of treating woolen textile material to reduce the feltingand shrinking tendencies thereof which consists in (1) impregnating saidtextile material with a composition comprising a reactive product ofpolymerization of a mixture containing, by weight, from about 5 to ofmaleic anhydride and about 95 to 85% of ethyl acrylate and (2) heatingthe resulting treated material at a temperature within the range ofabout 200 to 300 F. to cure the said polymerization product, said curedproduct being substantially water-insoluble.

6. A process of treating woolen fabric material to reduce the shrinkingtendencies thereof and to impart an improved finish thereto whichconsists in (l) impregnating said fabric material with a compositioncomprising a reactive product of polymerization of a mixture containing,by weight, from about 2 to of maleic anhydride and from about 98 to 80%of a lower alkyl ester of acrylic acid that contains from one to fourcarbon atoms, inclusive, in the alkyl grouping thereof, and (2) heatingthe resulting treated material at a temperature within the range ofabout 200 to 300 F. for a period sumcient to cure the saidpolymerization product substantially completely.

7. A protein-containing textile material which is resistant to feltingand shrinking and which is impregnated with a substantiallywater-insoluble composition comprising a product of polymerization of apolymerizable mixture including. by weight. from about 2 to 20% ofmaleic anhydride and from about 98 to of a lower alkyl ester of acrylicacid that contains from one to four carbon atoms, inclusive, in thealkyl grouping thereof, said composition being free from any compoundwhich is reactive with the said polymerization product.

8. A wool-containing textile material which is resistant to felting andshrinking and which is impregnated with a substantially water-insolublecomposition comprising a product of polymerization of a polymerizablemixture including, by weight, from about 5 to 15% of maleic anhydrldeand from about '95 to of ethyl acrylate, said composition being freefrom any compound which is reactive with the said polymerizationproduct.

9. A woolen textile material which is resistant to shrinking and whichis impregnated with at least about 2%, by weight of the untreatedmaterial, of a substantially water-insoluble composition comprising acopolymer which is the product of polymerization of a mixture containmg,by weight, from about 2 to 20% of maleic anhydride and from about 98 to80% of a lower alkyl ester of acrylic acid that contains from one totour carbon atoms, inclusive, in the alkyl grouping thereof, saidcomposition being free from any compoimdlwhich is reactive with the saidpolymerization product.

10. A woolen fabric materlabwhich is resistant to shrinking, has a softfeeling to the touch and which is impregnated with about 3 to 15%, byweight of the untreated material, of a substantially water-insolublecopolymer which is the product of polymerization of a polymerizablemixture of. by weight, from about 5 to 15% of maleic anhydride and fromabout 95 to 85% of ethyl acrylate.

11. Shrink-resistant wool which is impregnated and coated with about 3to 15%. by weight of the untreated wool, of a substantiallywaterinsoluble composition comprising a copolymer which is the productof polymerization of a polymerizable mixture of, by weight, about 10%maleic anhydride and about ethyl acrylate, said composition being freefrom any compound which is reactive with the said copolymer.

12. A protein-containing textile material which is resistant to feltingand shrinking and which is impregnated with a substantiallywater-insoluble composition consisting of a mixture, cured under heat insitu, of (l) a lower alkylated methylol melamine and (2) a reactiveproduct of polymerization of a polymerizable mixture including, byweight, from about 2 to 20% of malelc anhydride and from about 98 to 80%of a lower alkyl ester of acrylic acid that contains from one to fourcarbon atoms, inclusive, in the alkyl grouping thereof.

13, A process of treating a woolen fabric to reduce the shrinkingtendencies thereof and to impart an improved finish thereto, saidprocess consisting of (l) immersing the said fabric in a solution ofsoluble copolymer dissolved in an inert volatile organic liquid, saidcopolymer being a reactive product of polymerization of a mixture ofcomonomers consisting of, by weight, about 10% of maleic anhydride andabout 90% of ethyl acrylate and said solution containing about 10% byweight of the said copolvmer, (2) squeezing excess solution from theresulting fabric so as to obtain an impregnated woolen fabric whichcontains about 8 to 9% by weight, based on 13 the dry weight of the saidfabric, of the said 00- polymer, and (3) heating the squeezed fabric ata temperature of the order of 290 F. for a period suflicientiy long tovolatilize the organic liquid from the solution retained in the fabricand to cure the said copolymer, said copolymer in cured state beingsubstantially water-insoluble.

- EDWARD L. KROPA.

AR'I'HUR S. NYQUIST.

REFERENCES CITED Number 14 UNITED STATES PATENTS Name Date Voss July 14,1936 Voss May 30, 1939 Kaase Sept. 5, 1939 Johnstone Sept. 14, 1943Drey-i'us Sept. 19, 1944 Watson Apr. 23, 1946 Atwood Apr. 8, 1947 PowersMay 10, 1949

1. A PROCESS OF TREATING PROTEIN-CONTAINING TEXTILE MATERIAL TO REDUCETHE FELTING AND SHRINKING TENDENCIES THEREOF WHICH COMPRISES (1)TREATING SAID TEXTILE MATERIAL SOLELY WITH A COMPOSITION COMPRISING AREACTIVE PRODUCT OF POLYMERIZATION OF A POLYMERIZABLE MIXTURE INCLUDING,BY WEIGHT, FROM ABOUT 2 TO 20% OF MALEIC ANHYDRIDE AND FROM ABOUT 98 TO80% OF A LOWER ALKYL ESTER OF ACRYLIC ACID THAT CONTAINS FROM ONE TOFOUR CARBON ATOMS, INCLUSIVE, IN THE ALKYL GROUPING THEREOF, AND (2)HEATING THE RESULTING TREATED MATERIAL TO CURE THE SAID POLYMERICATIONPRODUCT.